CA1234145A - Preparation of carboxylic acids and esters thereof - Google Patents
Preparation of carboxylic acids and esters thereofInfo
- Publication number
- CA1234145A CA1234145A CA000439330A CA439330A CA1234145A CA 1234145 A CA1234145 A CA 1234145A CA 000439330 A CA000439330 A CA 000439330A CA 439330 A CA439330 A CA 439330A CA 1234145 A CA1234145 A CA 1234145A
- Authority
- CA
- Canada
- Prior art keywords
- acid
- ester
- ethylene
- formic acid
- olefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
Abstract
ABSTRACT OF THE DISCLOSURE
A carboxylic acid or an ester thereof having at least two carbon atoms more than formic acid is prepared by reacting at elevated temperature e.g.
100 to 250°C formic acid or a formate ester with an olefin e.g. ethylene in the presence of, as catalyst, a Group VIII noble metal e.g. iridium, preferably promoted by iodide, to cause addition of the formic acid or ester to the olefin and form the a higher acid e.g. propionic acid or ester thereof.
A strong acid such as a sulphonic acid may be used as a copromoter.
The catalyst is employed in solution.
A carboxylic acid or an ester thereof having at least two carbon atoms more than formic acid is prepared by reacting at elevated temperature e.g.
100 to 250°C formic acid or a formate ester with an olefin e.g. ethylene in the presence of, as catalyst, a Group VIII noble metal e.g. iridium, preferably promoted by iodide, to cause addition of the formic acid or ester to the olefin and form the a higher acid e.g. propionic acid or ester thereof.
A strong acid such as a sulphonic acid may be used as a copromoter.
The catalyst is employed in solution.
Description
~3~S 22935-748 PREPARATION OF CARBOXYLIC ACIDS AND ESTERS THEREOF
This invention relates to a process for the preparation of carboxylic acids or esters thereof by the reaction of formic acid or an ester thereof with an olefin in which the ~ormic acid or formate ester is added to the olefin to form a higher carboxylic acid or an ester thereof.
The addition o~ a formate ester to an olefin has been pre-viously described in United States Patent No. 3,849,456 in which the reaction is catalyzed by a peroxide~ The reaction is relatively un-selective in that it yields a broad mixture of carboxylic acid es-ters.
It has now been found th,at the addition of formic acid or an ester thereof to an olefin can be catalyzed by a nobel Group VIII
metal such as iridium which has the advantage that it yields a nar-rower mixture of carboxylic acid esters than the above mentioned pero~ide catalyzed reaction. Moreover, by appropriate adjustment of the reaction conditions it can be made highly selective in that for example the higher carboxylic acid an;d its ester product can exceed 90% by weight of the liquid phase product.
Thus, according to the present invention there is provided a process for preparing a carboxylic acid or an ester thereof, the c,arboxylic acid having at least two carbon atoms more than formic ac.id which comprises reacting~ at elevated temperature, formic acid or an ester thereof with an olefin in the presence of, as catalyst, an effective amount of a Group VIII noble metal, a halide promoter and a strong acid consisting of a mineral acid or a sulphonic acid to cause addition of the formic acid or ester to the olefin and form the acid or ester having at least two carbon atoms more than formic acld.
. . .
Conveniently the Group VIII noble metal is B co~pound which is preferably 601uble in the reactants and products under the reaction conditions.
By Group VIII noble metal we mean ruthenium, rhodium, palladium, ~ 5 06mium, iridium and platinum.
Preferably the Group VIII metal compound is an iridium compound for example a salt or complex such as [Ir(cyclooctadiene~Cl]2, Na2IrC16-XH20, ~IrCO[P(C6H5)3]3, ClIrCO(PEt3)2, IrC13.XH20, IrI3 XH20~Na3Ir(No2)6.XE~2o~ [(CsHs)2Ir]N03, Ir4(CO)12, IrH3[P(C6H5)3]3~ and (CgH12)2IrSnC13. Preferred compounds are [Ir(cyclooctadiene)Cl]2, IrC13.XH20, IrBr3.XH20, IrI3.XH20. and iridium trisacetylacetonate~ The symbol X indicates differing degrees of hydration and varies from 0 to 12. Metallic iridium can be employed.
P~eferably the halide pr~moter is~ en i~odide promoter.
Su1table iodide6 are alkyl lodides psrticularly lower alkyl iodides such as methyl iodide. Suitable amounts of iodide in relation to the Group VIII noble metal are from 1 to 500 moles for each mole of Group VIII noble metals.
When formic acid is a reactant, some of the iodide tends to be converted to a carboxylic acld by reaction with the formic acid. For example methyl iodide is converted to acetic acid. It is therefore preferred that the alkyl group of the lodide promoter is the same as that in the acid being formed a~ the reaction product. Thus lt is preferred to use ethyl iodide when producing prop~onic acid.
The reaction can be effected in either the gaseous or liquld phase . In the latter a solvent for the liquid reactants i8 conveniently employed. Suitable solvents are carboxylic acids of formula RC02H where R is Cl to C8 aliphatic, C4 to C8 cycloaliphatic, C7 to C12 aralkyl or C6 to C1o aryl.
' ~r.Se:~bhy A strong acid which is compatible with the catalyst i8 also present as a copromoter for the catalyst. By compatible is meant that the strong acid should not deactivate the catalyst. When the acid is present the iodide promoter can be Gmitted. By strong acld is 3 ~L23~
meant one which is significantly more acidic than the carboxylic acid employed as the solvent, for7~xample an acid having a ~;t pK of less than 0 (as measured in water). S~r~ strong acids are mineral acids and sulphonic acids such as p-toluene sulphonic acid and methane sulphonic acid employed in an amount, for example, of between 1.5 and 5.0% by wt. The concentration of acid may vary widely.
Usually concentrations up to 10% by wt are convenient, but a liquid sulphonic acld can for example be employed.
Suitable olefins for use in the present invention are those having from 2 to 30 carbon atoms of formula:
R1 - C = C - R4 in aliphatic heteroaliphatic, acyclic or cycloaliphatic form wherein R1~ R2, R3 and R4 are independently either hydrogen, halogen, alkyl, alkenyl, aryl, cycloalkyl or cycloalkenyl moieties or, in a heteroaliphatic compound, are moieties containing nitrogen, phosphorus, sulphur, halogen or oxygen atoms or, in a cycloaliphatic compound R2 and R3 are linked. Sultable compounds having the above formula include ethylene; propylene; butene-1; butene-2; pentenes;
hexenes; octenes; hexadecene; 2-methylpropene; styrene; 1,4-hexadiene;
acrolein; methyl vinyl ketone and 2-cyclohexylbutene. If desired, mixtures of the aforesaid oleins may be employed.
Suitable esters of formic acld are those of formula HC02R where R
is a C1 to C8 aliphatic group.
Conveniently the reaction i~ carried out at a temperature ln the range from 100 to 250C, preferably from 170 to 215C.
In the case of a gaseous olefln the pressure ls desirably at least 10 psi in excess of autogeneous pressure. Convenient pressures are in the range 200 to 1200 psi.
In order to reduce undesirable decomposition of formic acid the concentration of formic acid i8 preferably maintained low, for example 25~ by wt of the reaction aolution and the partial pressure of olefin ; high, for example in the case of ethylene greater than 300 p9i. In ; 35 reactions involving formate esters such as methyl formate, similar 4 ~L23~
conditions serve to reduce loss of selectivity due to isomerlsation of the methyl formate to acetic acid which is known to be catalysed under certain conditions by iodide promoted iridium.
Preferably the reaction is effected in the substantial absence of oxygen, although carbon monoxide or inert gases such as nitrogen or hydrogen can be present.
The products of the present invention have a wide variety of uses, for example, propionic acid is employed in agriculture as a preservative.
The invention is illustrated by the following Examples.
Example l - Reaction of methyl formate with ethylene In the examples all the reactants and products except the ethylene in Examples 1 to 5 and 7 to ll were added in the liquid phase, and the catalysts were employed ln solutlon.
lS The pressures reached inside the reactors were not measured in every case.
A corrosion resistant autoclave of 100 ml capacity equipped with rotary stirrer was charged with a reaction mixture comprising 15.2 g methyl formate, 8.1 g methyl iodide as promoter, 40.5 g acetic acid as solvent and 0.1 g IrC13. The autoclave was closed, flushed three times with ethylene, and pressurised wh~lst stirring with 400 psi ethylene. The autoclave was then heated and the temperature maintainad at 200C for 2.5 hours. After cooling and depressurlsation, the product was recovered and analysed ~y gas liquid chromatography (G.L.C.). It was found to contain by weight 13.5%
propionic acid9 2.5% methyl proplonate, 22.8% methyl acetate (formed by transesterification~, and 6.3% unreac~ed methyl formate.
Example 2 - Reaction of methyl formate with ethylene In this example propionic scid was employed as solvent in order to determine the amount of acetic acid formed under the condltions of Example 1.
To the autoclave of ~xample 1 was charged 15.0 g methyl formate, 9.0 g methyl iodide as promoter, 40.5 g propicnlc acid as solvent, and 0.1 g IrC13. The procedure of Example l wa5 then followed. Analysis of the product showed it to contaln only 0.8% acetic acld, trace 5 ~L~3~
quantities of methyl acetate, and 8.3% unreacted methyl formate.
Propionate was also formed but the amount produced could not be measured accurately because of the propionic acid solvent used.
This example demonstrates that under the conditions of ~xample 1 only small quantities of acetic acid are formed.
Comparison of Examples 1 and 2 shows that 95% of the liquid phase reaction product is propionate (i.e. propionic acid and eæter).
Example 3 - Reaction of methyl formate with ethylene using a strong acld as copromoter.
A 500 ml corrosion resistant autoclave equipped with a rotary stirring system was charged with a reaction mixture comprislng the following: methyl formate 120 g, acetic acld 102 g as solvent, methyl iodide 48 g as promoter, ~ridium trichloride 0.4 g, and p-toluene sùlphonic acid 12 g as copromoter. The autoclave was sealed, flushed three times with ethylene, and was then pressurised, whilst stirring, with 400 psi ethylene. The autorlave was then heated to 200C, and held at this temperatur~ for 30 m~nutesO After cooling and depressurising, the product was recovered and analysed by G.L.C. It contained by ~eight 10% propionic acid, 12.7% methyl propionate, 24.9%
~ethyl acetate and 10.5% unreacted methyl formate.
- Reaction of methyl formate with ethylene.
Example 3 was repeated, except with the p-~oluene sulphonic acid copromoter absent. The product was foùnd to contain only 4.0%
propionic acid and 1.4% methyl propionate, together with 18.7~ methyl acetate and 24.3~ unreacted methyl formate.
Co~parison of Examples 3 and 4 show that the a higher yield of propionic acid and its ester are obtained when the strong acid is included in the reaction mlxture.
Example 5 - Reaction of methyl formate with ethylene The autoclave of ~xample 1 was charged with 30.0g methyl formate, 25.0g acetic acid as solvent, 12.6g methyl lodide a~ promoter, 3.0g p-toluene sulphonic acid as copromoter and 0.1g ruthenium trichloride. The autoclave was flu~hed three times with ethylene, ~ealed, and pressurised whilst stirring with 400 p8i ethylene. The reactor was heated to 200C for 3 hours, cooled, and the contents 6 1.;~3~
removed. Analysls by G.L.C. showed the product to contain 0.65% wt ~ethyl propionate and 0.4% wt propionic acid.
Example 6 - Reaction of ~ethyl formate with hexene-l The autoclave of Example 3 was charged wi~h 60.0g hex-l-ene, 60.0g methyl formate, 120.0g propionic acid as solvent, 47.9g methyl iodide as promoter, 12.0g p-toluene sulphonic acid as copromoter, and 0.395g iridium trichloride. The autoclave was flushed three times with nitrogen, sealed, and heated to 200C. A~ter 6 hours at this temperature the reactor was cooled, and the product analysed by G.L.C. It was found to contain by weight 4.5% methyl heptanoate and 6.5% heptanoic acid.
Example 7 - Reaction of formic acid with ethylene A 500 ~l corrosion-resistant autoclave was charged with 50.9 g for~ic acid solution (90% by weight in water), 29.8 g ~ethyl iodide as promoter, 0.417 g iridium trichloride and 150.7 g acetic acid as solvent. The autoclave was sealed, flushed three times with ethylene, and then pressurised with 650 psi ethylene whilst stlrring. The reactor was heated to 200C and held at this temperature for 1~ hours before cooling. Gas liquid chromatography (GLC) analys~s showed the product to contain, by weight, 12.6% propionic acid.
Example 8 - Reaction of for~ic acid with ethylene The autoclave of Example 7 was charged with 50.0 g formic acid Golutlon (90% by weight in water), 29.5 ethyl iodide as promoter, 0.404 g iridium trichlorlde, 149.8 g acetlc acid as solvent and 12.3 g methane ~ulphonic acid as copromoter. The autoclave was flushed three timefi with ethylene, sealed, and pressurised with 600 psi ethylene whilst stirring. The reactor was heated, and held at 200C for 30 minutes before cooling. GLC analysis of the product showed it to contain, by weight, 22.4% propionic acid.
In this example the alkyl group of the copromoter was the same as that in the propionic acid product.
Example 9 - Reaction of formic acid with ethylene in the absence of carboxylic acid solvent A 100 ml corrosion resistant autoclave was charged with 40.5 g formic acid solution (90% by weight in water), 7.6 g methyl iodlde as ~3~5 promoter and 0.103 g iridium erichloride. The autoclave was sealed~
flushed three tlmes with ethylene and pressurised with 400 p9i ethylene whilst stirring. The reactor was heated and held at 200C
for 1~ hours before cooling. CLC analysis of the product was carried out, and showed lt to contain 20.9% by weight of propio~ic acid.
Example 10 - Reaction of methyl formate with ethylene in the absence of a carboxylic acid solvent.
The autoclave of example 1 was charged with 35.0g methyl formate, 5.6g methyl iodide as promoter, 4.g p-toluene sulphonic acid as copromoter, and 0.1g irldium trichloride. The autoclave was flushed several times with ethylene, pressurised with 400 psia ethylene, sealed, and heated at 200C for 1 hour. Durlng this period the pressure did not rise above 700 psia~ The autoclave was then cooled, and the product recovered and analysed by GLC. It was found to contain by weight 17.8% methyl propionate, 7.8% methyl acetate, 1,5%
propionic acid, and 1.1% acetic acid.
This example together with Examples 11 and 12 below demonstrate that a carboxylic acid solvent is not required when a strong acid is employed.
Example 11 - Reaction of methyl formate wlth ethylene The autoclave of example 1 was charged with 35.0g methyl formate, 5.5g methyl iodideas promoter, 4.0g methane sulphonic acld as copromoterl and 0.139g iridium trisacetylacetonate. The procedure of example 10 was then followed, except that the reaction time at 200C
was t hour. The product was found to contain by weight 21.6% methyl propionate, 7.8% propionic acid, 11~8% methyl acetate and 5.0% acetic acid.
Example 12 - Reaction of methyl formate with hex-l-ene in the absence of solvent The autoclave of example 1 was charged with 15.0g methyl formate, 25.0 hex-1-ene, 5.0g methyl iodide as promoter, 4.0g methane sulphonic acid as copromoter, and 0.106g iridium trichloride. The autoclave was then flushed several times with nitrogen ant pressuri~ed with 300 psia nitrogen. The reaction mixture was then heated to 200C and this temperature maintained for 3 hours; during which time the pressure did 8 ~3~
not exceed 650 psi. The autoclave was then cooled and the product analysed by GLC. It was found to contain by weight ca. 26~ methyl n-heptanoatP, ca~ 10% methyl i-heptanoate, ca. 3.$% hexyl hep~a~oate (and isomers), ca. 8% n-heptanolc acid and ca. 3% i-heptanoic acid.
-
This invention relates to a process for the preparation of carboxylic acids or esters thereof by the reaction of formic acid or an ester thereof with an olefin in which the ~ormic acid or formate ester is added to the olefin to form a higher carboxylic acid or an ester thereof.
The addition o~ a formate ester to an olefin has been pre-viously described in United States Patent No. 3,849,456 in which the reaction is catalyzed by a peroxide~ The reaction is relatively un-selective in that it yields a broad mixture of carboxylic acid es-ters.
It has now been found th,at the addition of formic acid or an ester thereof to an olefin can be catalyzed by a nobel Group VIII
metal such as iridium which has the advantage that it yields a nar-rower mixture of carboxylic acid esters than the above mentioned pero~ide catalyzed reaction. Moreover, by appropriate adjustment of the reaction conditions it can be made highly selective in that for example the higher carboxylic acid an;d its ester product can exceed 90% by weight of the liquid phase product.
Thus, according to the present invention there is provided a process for preparing a carboxylic acid or an ester thereof, the c,arboxylic acid having at least two carbon atoms more than formic ac.id which comprises reacting~ at elevated temperature, formic acid or an ester thereof with an olefin in the presence of, as catalyst, an effective amount of a Group VIII noble metal, a halide promoter and a strong acid consisting of a mineral acid or a sulphonic acid to cause addition of the formic acid or ester to the olefin and form the acid or ester having at least two carbon atoms more than formic acld.
. . .
Conveniently the Group VIII noble metal is B co~pound which is preferably 601uble in the reactants and products under the reaction conditions.
By Group VIII noble metal we mean ruthenium, rhodium, palladium, ~ 5 06mium, iridium and platinum.
Preferably the Group VIII metal compound is an iridium compound for example a salt or complex such as [Ir(cyclooctadiene~Cl]2, Na2IrC16-XH20, ~IrCO[P(C6H5)3]3, ClIrCO(PEt3)2, IrC13.XH20, IrI3 XH20~Na3Ir(No2)6.XE~2o~ [(CsHs)2Ir]N03, Ir4(CO)12, IrH3[P(C6H5)3]3~ and (CgH12)2IrSnC13. Preferred compounds are [Ir(cyclooctadiene)Cl]2, IrC13.XH20, IrBr3.XH20, IrI3.XH20. and iridium trisacetylacetonate~ The symbol X indicates differing degrees of hydration and varies from 0 to 12. Metallic iridium can be employed.
P~eferably the halide pr~moter is~ en i~odide promoter.
Su1table iodide6 are alkyl lodides psrticularly lower alkyl iodides such as methyl iodide. Suitable amounts of iodide in relation to the Group VIII noble metal are from 1 to 500 moles for each mole of Group VIII noble metals.
When formic acid is a reactant, some of the iodide tends to be converted to a carboxylic acld by reaction with the formic acid. For example methyl iodide is converted to acetic acid. It is therefore preferred that the alkyl group of the lodide promoter is the same as that in the acid being formed a~ the reaction product. Thus lt is preferred to use ethyl iodide when producing prop~onic acid.
The reaction can be effected in either the gaseous or liquld phase . In the latter a solvent for the liquid reactants i8 conveniently employed. Suitable solvents are carboxylic acids of formula RC02H where R is Cl to C8 aliphatic, C4 to C8 cycloaliphatic, C7 to C12 aralkyl or C6 to C1o aryl.
' ~r.Se:~bhy A strong acid which is compatible with the catalyst i8 also present as a copromoter for the catalyst. By compatible is meant that the strong acid should not deactivate the catalyst. When the acid is present the iodide promoter can be Gmitted. By strong acld is 3 ~L23~
meant one which is significantly more acidic than the carboxylic acid employed as the solvent, for7~xample an acid having a ~;t pK of less than 0 (as measured in water). S~r~ strong acids are mineral acids and sulphonic acids such as p-toluene sulphonic acid and methane sulphonic acid employed in an amount, for example, of between 1.5 and 5.0% by wt. The concentration of acid may vary widely.
Usually concentrations up to 10% by wt are convenient, but a liquid sulphonic acld can for example be employed.
Suitable olefins for use in the present invention are those having from 2 to 30 carbon atoms of formula:
R1 - C = C - R4 in aliphatic heteroaliphatic, acyclic or cycloaliphatic form wherein R1~ R2, R3 and R4 are independently either hydrogen, halogen, alkyl, alkenyl, aryl, cycloalkyl or cycloalkenyl moieties or, in a heteroaliphatic compound, are moieties containing nitrogen, phosphorus, sulphur, halogen or oxygen atoms or, in a cycloaliphatic compound R2 and R3 are linked. Sultable compounds having the above formula include ethylene; propylene; butene-1; butene-2; pentenes;
hexenes; octenes; hexadecene; 2-methylpropene; styrene; 1,4-hexadiene;
acrolein; methyl vinyl ketone and 2-cyclohexylbutene. If desired, mixtures of the aforesaid oleins may be employed.
Suitable esters of formic acld are those of formula HC02R where R
is a C1 to C8 aliphatic group.
Conveniently the reaction i~ carried out at a temperature ln the range from 100 to 250C, preferably from 170 to 215C.
In the case of a gaseous olefln the pressure ls desirably at least 10 psi in excess of autogeneous pressure. Convenient pressures are in the range 200 to 1200 psi.
In order to reduce undesirable decomposition of formic acid the concentration of formic acid i8 preferably maintained low, for example 25~ by wt of the reaction aolution and the partial pressure of olefin ; high, for example in the case of ethylene greater than 300 p9i. In ; 35 reactions involving formate esters such as methyl formate, similar 4 ~L23~
conditions serve to reduce loss of selectivity due to isomerlsation of the methyl formate to acetic acid which is known to be catalysed under certain conditions by iodide promoted iridium.
Preferably the reaction is effected in the substantial absence of oxygen, although carbon monoxide or inert gases such as nitrogen or hydrogen can be present.
The products of the present invention have a wide variety of uses, for example, propionic acid is employed in agriculture as a preservative.
The invention is illustrated by the following Examples.
Example l - Reaction of methyl formate with ethylene In the examples all the reactants and products except the ethylene in Examples 1 to 5 and 7 to ll were added in the liquid phase, and the catalysts were employed ln solutlon.
lS The pressures reached inside the reactors were not measured in every case.
A corrosion resistant autoclave of 100 ml capacity equipped with rotary stirrer was charged with a reaction mixture comprising 15.2 g methyl formate, 8.1 g methyl iodide as promoter, 40.5 g acetic acid as solvent and 0.1 g IrC13. The autoclave was closed, flushed three times with ethylene, and pressurised wh~lst stirring with 400 psi ethylene. The autoclave was then heated and the temperature maintainad at 200C for 2.5 hours. After cooling and depressurlsation, the product was recovered and analysed ~y gas liquid chromatography (G.L.C.). It was found to contain by weight 13.5%
propionic acid9 2.5% methyl proplonate, 22.8% methyl acetate (formed by transesterification~, and 6.3% unreac~ed methyl formate.
Example 2 - Reaction of methyl formate with ethylene In this example propionic scid was employed as solvent in order to determine the amount of acetic acid formed under the condltions of Example 1.
To the autoclave of ~xample 1 was charged 15.0 g methyl formate, 9.0 g methyl iodide as promoter, 40.5 g propicnlc acid as solvent, and 0.1 g IrC13. The procedure of Example l wa5 then followed. Analysis of the product showed it to contaln only 0.8% acetic acld, trace 5 ~L~3~
quantities of methyl acetate, and 8.3% unreacted methyl formate.
Propionate was also formed but the amount produced could not be measured accurately because of the propionic acid solvent used.
This example demonstrates that under the conditions of ~xample 1 only small quantities of acetic acid are formed.
Comparison of Examples 1 and 2 shows that 95% of the liquid phase reaction product is propionate (i.e. propionic acid and eæter).
Example 3 - Reaction of methyl formate with ethylene using a strong acld as copromoter.
A 500 ml corrosion resistant autoclave equipped with a rotary stirring system was charged with a reaction mixture comprislng the following: methyl formate 120 g, acetic acld 102 g as solvent, methyl iodide 48 g as promoter, ~ridium trichloride 0.4 g, and p-toluene sùlphonic acid 12 g as copromoter. The autoclave was sealed, flushed three times with ethylene, and was then pressurised, whilst stirring, with 400 psi ethylene. The autorlave was then heated to 200C, and held at this temperatur~ for 30 m~nutesO After cooling and depressurising, the product was recovered and analysed by G.L.C. It contained by ~eight 10% propionic acid, 12.7% methyl propionate, 24.9%
~ethyl acetate and 10.5% unreacted methyl formate.
- Reaction of methyl formate with ethylene.
Example 3 was repeated, except with the p-~oluene sulphonic acid copromoter absent. The product was foùnd to contain only 4.0%
propionic acid and 1.4% methyl propionate, together with 18.7~ methyl acetate and 24.3~ unreacted methyl formate.
Co~parison of Examples 3 and 4 show that the a higher yield of propionic acid and its ester are obtained when the strong acid is included in the reaction mlxture.
Example 5 - Reaction of methyl formate with ethylene The autoclave of ~xample 1 was charged with 30.0g methyl formate, 25.0g acetic acid as solvent, 12.6g methyl lodide a~ promoter, 3.0g p-toluene sulphonic acid as copromoter and 0.1g ruthenium trichloride. The autoclave was flu~hed three times with ethylene, ~ealed, and pressurised whilst stirring with 400 p8i ethylene. The reactor was heated to 200C for 3 hours, cooled, and the contents 6 1.;~3~
removed. Analysls by G.L.C. showed the product to contain 0.65% wt ~ethyl propionate and 0.4% wt propionic acid.
Example 6 - Reaction of ~ethyl formate with hexene-l The autoclave of Example 3 was charged wi~h 60.0g hex-l-ene, 60.0g methyl formate, 120.0g propionic acid as solvent, 47.9g methyl iodide as promoter, 12.0g p-toluene sulphonic acid as copromoter, and 0.395g iridium trichloride. The autoclave was flushed three times with nitrogen, sealed, and heated to 200C. A~ter 6 hours at this temperature the reactor was cooled, and the product analysed by G.L.C. It was found to contain by weight 4.5% methyl heptanoate and 6.5% heptanoic acid.
Example 7 - Reaction of formic acid with ethylene A 500 ~l corrosion-resistant autoclave was charged with 50.9 g for~ic acid solution (90% by weight in water), 29.8 g ~ethyl iodide as promoter, 0.417 g iridium trichloride and 150.7 g acetic acid as solvent. The autoclave was sealed, flushed three times with ethylene, and then pressurised with 650 psi ethylene whilst stlrring. The reactor was heated to 200C and held at this temperature for 1~ hours before cooling. Gas liquid chromatography (GLC) analys~s showed the product to contain, by weight, 12.6% propionic acid.
Example 8 - Reaction of for~ic acid with ethylene The autoclave of Example 7 was charged with 50.0 g formic acid Golutlon (90% by weight in water), 29.5 ethyl iodide as promoter, 0.404 g iridium trichlorlde, 149.8 g acetlc acid as solvent and 12.3 g methane ~ulphonic acid as copromoter. The autoclave was flushed three timefi with ethylene, sealed, and pressurised with 600 psi ethylene whilst stirring. The reactor was heated, and held at 200C for 30 minutes before cooling. GLC analysis of the product showed it to contain, by weight, 22.4% propionic acid.
In this example the alkyl group of the copromoter was the same as that in the propionic acid product.
Example 9 - Reaction of formic acid with ethylene in the absence of carboxylic acid solvent A 100 ml corrosion resistant autoclave was charged with 40.5 g formic acid solution (90% by weight in water), 7.6 g methyl iodlde as ~3~5 promoter and 0.103 g iridium erichloride. The autoclave was sealed~
flushed three tlmes with ethylene and pressurised with 400 p9i ethylene whilst stirring. The reactor was heated and held at 200C
for 1~ hours before cooling. CLC analysis of the product was carried out, and showed lt to contain 20.9% by weight of propio~ic acid.
Example 10 - Reaction of methyl formate with ethylene in the absence of a carboxylic acid solvent.
The autoclave of example 1 was charged with 35.0g methyl formate, 5.6g methyl iodide as promoter, 4.g p-toluene sulphonic acid as copromoter, and 0.1g irldium trichloride. The autoclave was flushed several times with ethylene, pressurised with 400 psia ethylene, sealed, and heated at 200C for 1 hour. Durlng this period the pressure did not rise above 700 psia~ The autoclave was then cooled, and the product recovered and analysed by GLC. It was found to contain by weight 17.8% methyl propionate, 7.8% methyl acetate, 1,5%
propionic acid, and 1.1% acetic acid.
This example together with Examples 11 and 12 below demonstrate that a carboxylic acid solvent is not required when a strong acid is employed.
Example 11 - Reaction of methyl formate wlth ethylene The autoclave of example 1 was charged with 35.0g methyl formate, 5.5g methyl iodideas promoter, 4.0g methane sulphonic acld as copromoterl and 0.139g iridium trisacetylacetonate. The procedure of example 10 was then followed, except that the reaction time at 200C
was t hour. The product was found to contain by weight 21.6% methyl propionate, 7.8% propionic acid, 11~8% methyl acetate and 5.0% acetic acid.
Example 12 - Reaction of methyl formate with hex-l-ene in the absence of solvent The autoclave of example 1 was charged with 15.0g methyl formate, 25.0 hex-1-ene, 5.0g methyl iodide as promoter, 4.0g methane sulphonic acid as copromoter, and 0.106g iridium trichloride. The autoclave was then flushed several times with nitrogen ant pressuri~ed with 300 psia nitrogen. The reaction mixture was then heated to 200C and this temperature maintained for 3 hours; during which time the pressure did 8 ~3~
not exceed 650 psi. The autoclave was then cooled and the product analysed by GLC. It was found to contain by weight ca. 26~ methyl n-heptanoatP, ca~ 10% methyl i-heptanoate, ca. 3.$% hexyl hep~a~oate (and isomers), ca. 8% n-heptanolc acid and ca. 3% i-heptanoic acid.
-
Claims (10)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing a carboxylic acid or an ester thereof, the carboxylic acid having at least two carbon atoms more than formic acid which comprises reacting, at elevated temperature, formic acid or an ester thereof with an olefin in the presence of, as catalyst, an effective amount of a Group VIII noble metal, a halide promoter and a strong acid consisting of a mineral acid or a sulphonic acid to cause addition of the formic acid or ester to the olefin and form the acid or ester having at least two carbon atoms more than formic acid.
2. A process as claimed in claim 1 wherein the Group VIII
noble metal is iridium.
noble metal is iridium.
3. A process as claimed in claim 1 wherein the halide promo-ter is an iodide promoter.
4. A process as claimed in claim 3 wherein the halide promo-ter is an alkyl iodide.
5. A process as claimed in claim 3 or 4 wherein the carboxylic acid having at least 2 carbon atoms more than formic acid is of for-mula RCO2H and the halide promoter is of formula RX where X is hali-de and the R groups of the acid and halide are identical.
6. A process as claimed in claim 1, 2 or 3 wherein the sul-phonic acid is methane sulphonic acid or p-toluene sulphonic acid.
7. A process as claimed in claim 1, 2 or 3 wherein the reac-tion is carried out at a temperature in the range 100 to 250°C and at a pressure in the range 200 to 1200 psi.
8. A process as claimed in claim 1 wherein the process is operated in the liquid phase and a solvent for the liquid reactants and products is employed.
9. A process as claimed in claim 8 wherein the solvent is a carboxylic acid.
10. A process as claimed in claim 1, 2 or 3 wherein the olefin is ethylene.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8229988 | 1982-10-20 | ||
| GB8229988 | 1982-10-20 | ||
| GB838300888A GB8300888D0 (en) | 1983-01-13 | 1983-01-13 | Carboxylic acids |
| GB8300888 | 1983-01-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1234145A true CA1234145A (en) | 1988-03-15 |
Family
ID=26284183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000439330A Expired CA1234145A (en) | 1982-10-20 | 1983-10-19 | Preparation of carboxylic acids and esters thereof |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4614816A (en) |
| EP (1) | EP0106656B1 (en) |
| AU (1) | AU569479B2 (en) |
| CA (1) | CA1234145A (en) |
| DE (1) | DE3366317D1 (en) |
| NO (1) | NO157414C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8328905D0 (en) * | 1983-10-28 | 1983-11-30 | Bp Chem Int Ltd | Carboxylic acid and esters |
| GB8521547D0 (en) * | 1985-08-29 | 1985-10-02 | British Petroleum Co Plc | Production of esters |
| US5034161A (en) * | 1988-07-18 | 1991-07-23 | Petrolite Corporation | Synthesis of aryl-substituted aliphatic acids |
| FR2659965B1 (en) * | 1990-03-26 | 1992-06-05 | Norsolor Sa | CATALYST AND METHOD FOR THE SYNTHESIS OF SATURATED CARBOXYL ESTERS. |
| FR2796639A1 (en) * | 1999-07-21 | 2001-01-26 | Rhodia Chimie Sa | PROCESS FOR THE PREPARATION OF A CARBOXYLIC ACID |
| CN102471219B (en) * | 2009-07-31 | 2016-05-25 | 日立化成株式会社 | The manufacture method of ester compounds |
| DE102011089008B4 (en) * | 2011-12-19 | 2017-08-24 | Evonik Degussa Gmbh | Process for the preparation of esters of formates and olefinically unsaturated compounds |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2013338A (en) * | 1931-08-24 | 1935-09-03 | Du Pont | Process for the production of carboxylic acids |
| US3470219A (en) * | 1964-01-30 | 1969-09-30 | Celanese Corp | Transaddition reaction between an olefin and a saturated aliphatic monocarboxylic acid |
| FR1484367A (en) * | 1965-07-22 | 1967-06-09 | Distillers Co Yeast Ltd | Process for the production of new organic acids |
| US3637478A (en) * | 1968-04-03 | 1972-01-25 | Armour Ind Chem Co | Process for production of aliphatic acids |
| US3816489A (en) * | 1968-08-15 | 1974-06-11 | Monsanto Co | Increasing the selectivity and yield in the production of carboxylic acids |
| NL184614C (en) * | 1972-03-06 | 1989-09-18 | Monsanto Co | PROCESS FOR THE PREPARATION OF PROPIONIC ACID AND / OR PROPIONIC ACID ANHYDRIDE. |
| US3849456A (en) * | 1972-03-22 | 1974-11-19 | Union Carbide Corp | Preparation of methyl alkanoates |
| JPS5912656B2 (en) * | 1980-03-22 | 1984-03-24 | 三菱瓦斯化学株式会社 | Production method of pentenoic acid ester |
| US4414409A (en) * | 1981-12-21 | 1983-11-08 | E. I. Du Pont De Nemours & Company | Palladium sulfonate catalyst systems for carbonylation of olefins |
| CA1239937A (en) * | 1982-04-12 | 1988-08-02 | Exxon Research And Engineering Company | Process for converting olefins to carboxylic acids or esters using soluble iridium compounds |
-
1983
- 1983-10-12 DE DE8383306161T patent/DE3366317D1/en not_active Expired
- 1983-10-12 EP EP83306161A patent/EP0106656B1/en not_active Expired
- 1983-10-13 US US06/541,379 patent/US4614816A/en not_active Expired - Fee Related
- 1983-10-19 AU AU20418/83A patent/AU569479B2/en not_active Ceased
- 1983-10-19 NO NO833806A patent/NO157414C/en unknown
- 1983-10-19 CA CA000439330A patent/CA1234145A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AU2041883A (en) | 1984-05-03 |
| NO157414B (en) | 1987-12-07 |
| AU569479B2 (en) | 1988-02-04 |
| US4614816A (en) | 1986-09-30 |
| NO157414C (en) | 1988-03-16 |
| DE3366317D1 (en) | 1986-10-23 |
| EP0106656A1 (en) | 1984-04-25 |
| EP0106656B1 (en) | 1986-09-17 |
| NO833806L (en) | 1984-04-24 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |